WO2019185938A2 - Nouvelle utilisation des chroman-6-ols substitués à chaînes latérales lipophiles étendues - Google Patents

Nouvelle utilisation des chroman-6-ols substitués à chaînes latérales lipophiles étendues Download PDF

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Publication number
WO2019185938A2
WO2019185938A2 PCT/EP2019/058117 EP2019058117W WO2019185938A2 WO 2019185938 A2 WO2019185938 A2 WO 2019185938A2 EP 2019058117 W EP2019058117 W EP 2019058117W WO 2019185938 A2 WO2019185938 A2 WO 2019185938A2
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Prior art keywords
oil
alkyl
substituents
acid
methyl
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PCT/EP2019/058117
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English (en)
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WO2019185938A3 (fr
Inventor
Laure CLASADONTE
André DUESTERLOH
Weerasinghe INDRASENA
Thomas Netscher
René Tobias STEMMLER
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Dsm Ip Assets B.V.
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Priority to BR112020019757-2A priority Critical patent/BR112020019757A2/pt
Priority to PE2020001504A priority patent/PE20211652A1/es
Priority to US17/041,910 priority patent/US11447459B2/en
Priority to EP19715068.3A priority patent/EP3774758A2/fr
Publication of WO2019185938A2 publication Critical patent/WO2019185938A2/fr
Publication of WO2019185938A3 publication Critical patent/WO2019185938A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
    • C07D311/58—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4
    • C07D311/70—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring other than with oxygen or sulphur atoms in position 2 or 4 with two hydrocarbon radicals attached in position 2 and elements other than carbon and hydrogen in position 6
    • C07D311/72—3,4-Dihydro derivatives having in position 2 at least one methyl radical and in position 6 one oxygen atom, e.g. tocopherols

Definitions

  • the present invention is directed towards the use of a compound of formula (I) as antioxidant,
  • one of the two substituents R 1 and R 2 is C 12-21 -alkyl and the other of the two substituents R 1 and R 2 is either hydrogen or Ci- 5 -alkyl or (CH 2 ) n -OH with n being an integer from 1 to 5, and
  • A is CH(R 3 )
  • R 3 , R 4 and R 6 are independently from each other H or Ci- 4 -alkyl, and wherein R 5 is H or OH or Ci- 4 -alkyl or Ci- 4 -alkoxy;
  • R 4 , R 5 and R 6 are not methyl, when R 3 is H, and one of the substituents R 1 and R 2 is methyl and the other of the two substituents R 1 and R 2 is C 12-21 -alkyl.
  • proviso compounds of formula (I) with at least two of R 4 , R 5 and R 6 being methyl, R 3 being H and one of the two substituents R 1 and R 2 being methyl and the other of the two substituents R 1 and R 2 being C 12-21 -alkyl are not encompassed by formula (I).
  • one of the two substituents R 1 and R 2 is methyl and the other of the two substituents R 1 and R 2 is 4,8,12- trimethyltridecyl
  • the compound is selected from alpha-tocopherol, beta- tocopherol and gamma-tocopherol, and thus, not encompassed by formula
  • the compounds of the present invention are efficient as antioxidants, preferably in feed and feed ingredients.
  • the compounds of the present invention are especially efficient as antioxidants in feed comprising proteins and/or unsaturated fatty acid (derivative)s and in feed ingredients comprising proteins and/or unsaturated fatty acid (derivative)s.
  • “Derivatives” are e.g. the monoglycerides, diglycerides and triglycerides as well as Ci- 6 -alkyl esters such as the methyl and ethyl esters.
  • the compound is selected from alpha-tocopherol, beta-tocopherol and gamma-tocopherol, and these compounds may still be present as additional antioxidants in the feed and feed ingredients of the present invention.
  • Unmodified fish meal can spontaneously combust from heat generated by oxidation of the polyunsaturated fatty acids in the fish meal.
  • factory ships have sunk because of such fires.
  • Strict rules regarding the safe transport of fish meal have been put in place by authorities and the International Maritime Organization (IMO).
  • IMO International Maritime Organization
  • fishmeal must be stabilized with antioxidants to prevent spontaneous combustion during overseas transport and storage.
  • the shipping regulations of the United Nations for the Transport of Dangerous Goods (UN-TDG) currently only allow ethoxyquin and BHT as antioxidants to stabilize fish meal for marine transport. But authorization of ethoxyquin has now been suspended in the European Union due to safety and health concerns.
  • BHT must be added in higher quantities to achieve the same efficacy as ethoxyquin. Furthermore, BHT is currently under safety evaluation by ECHA and its re-registration as feed additive is pending in Europe. Therefore, there is a need to replace ethoxyquin and BHT as an antioxidant.
  • one of the two substituents R 1 and R 2 is C12-21 -alkyl and the other of the two substituents R 1 and R 2 is either hydrogen or Ci-5-alkyl or (CH 2 ) n -OH with n being an integer from 1 to 5, and
  • A is CH(R 3 )
  • R 3 , R 4 and R 6 are independently from each other H or Ci- 4 -alkyl, and wherein R 5 is H or OH or Ci- 4 -alkyl or Ci- 4 -alkoxy; with the proviso that at least two of R 4 , R 5 and R 6 are not methyl, when R 3 is H and one of the substituents R 1 and R 2 is methyl and the other of the two substituents R 1 and R 2 is C12-21 -alkyl; and with the preferences for the substituents R 1 to R 6 as given below.
  • the compounds of formula (I) with the preferences as given below are not only suitable for stabilizing fish meal, but they are also suitable for stabilizing feed ingredients and feed. Preferences for feed ingredients and feed are given below.
  • alkyl and“alkoxy” in the context of the present invention encompass linear alkyl and branched alkyl, and linear alkoxy and branched alkoxy, respectively.
  • one of the two substituents R 1 and R 2 is C12-21 -alkyl, preferably one of the two substituents R 1 and R 2 is linear or branched Ci5 -2 o-alkyl, more preferably one of the two substituents R 1 and R 2 is linear or branched Ci 6 -i 8 -alkyl, most preferably one of the two substituents R 1 and R 2 is 4,8, 12-trimethyltridecyl, and the other of the two substituents R 1 and R 2 is either hydrogen or C1-5- alkyl, and
  • R 3 , R 4 and R 6 are independently from each other H or Ci- 4 -alkyl
  • R 5 is H or OH or Ci- 4 -alkyl or Ci- 4 -alkoxy
  • R 4 , R 5 and R 6 are not methyl, when R 3 is H and one of the substituents R 1 and R 2 is methyl and the other of the two substituents R 1 and R 2 is C12-21 -alkyl.
  • one of the two substituents R 1 and R 2 is C12-21 -alkyl, preferably one of the two substituents R 1 and R 2 is linear or branched Cis- 2 o-alkyl, more preferably one of the two substituents R 1 and R 2 is linear or branched Ci 6 -i 8 -alkyl, most preferably one of the two substituents R 1 and R 2 is 4,8,12-trimethyltridecyl, and
  • R 1 and R 2 is either hydrogen or methyl or ethyl
  • R 3 and R 4 are independently from each other H or methyl or ethyl, and R 6 is H or Ci- 4 -alkyl, preferably R 6 is H or methyl or ethyl, and
  • R 5 is H or OH or methyl or ethyl or methoxy or ethoxy
  • one of the two substituents R 1 and R 2 is C 12-21 -alkyl, preferably one of the two substituents R 1 and R 2 is linear or branched Cis- 2 o-alkyl, more preferably one of the two substituents R 1 and R 2 is linear or branched Ci 6 -i 8 -alkyl, most preferably one of the two substituents R 1 and R 2 is 4,8,12-trimethyltridecyl, and the other of the two substituents R 1 and R 2 is either hydrogen or methyl, and
  • R 3 is H
  • R 4 is H or methyl
  • R 6 is H or Ci- 4 -alkyl, preferably R 6 is H or methyl or ethyl, and
  • R 5 is H or OH or methyl or methoxy; with the proviso that at least two of R 4 , R 5 and R 6 are not methyl, when R 3 is H and one of the substituents R 1 and R 2 is methyl and the other of the two substituents R 1 and R 2 is C 12-21 -alkyl.
  • one of the two substituents R 1 and R 2 is C 12-21 -alkyl, preferably one of the two substituents R 1 and R 2 is linear or branched Cis- 2 o-alkyl, more preferably one of the two substituents R 1 and R 2 is linear or branched Ci 6 -i 8 -alkyl, most preferably one of the two substituents R 1 and R 2 is 4,8,12-trimethyltridecyl, and the other of the two substituents R 1 and R 2 is methyl, and
  • R 3 is H, and R 4 and R 5 are independently from each other H or methyl, R 6 is
  • R 6 is H or methyl or ethyl
  • one of the two substituents R 1 and R 2 is C 12-21 -alkyl, preferably one of the two substituents R 1 and R 2 is linear or branched Cis- 2 o-alkyl, more preferably one of the two substituents R 1 and R 2 is linear or branched Ci 6 -i 8 -alkyl, most preferably one of the two substituents R 1 and R 2 is 4,8,12-trimethyltridecyl, and the other of the two substituents R 1 and R 2 is methyl, and
  • R 3 and R 4 are H, and R 5 is H or methyl, and R 6 is H or Ci- 4 -alkyl, preferably R 6 is H or methyl or ethyl.
  • one of the two substituents R 1 and R 2 is C12-21 -alkyl, preferably one of the two substituents R 1 and R 2 is linear or branched Ci5- 20 -alkyl, more preferably one of the two substituents R 1 and R 2 is linear or branched Ci 6 -i 8 -alkyl, most preferably one of the two substituents R 1 and R 2 is 4,8,12-trimethyltridecyl, and
  • R 3 , R 4 and R 5 are H, and R 6 is H or Ci- 4 -alkyl, preferably R 6 is H or methyl, more preferably R 6 is methyl.
  • the compounds of the present invention are efficient as antioxidants, preferably in feed and feed ingredients.
  • Non-limiting examples of feed are pet food, feed for aquatic animals, feed for terrestrial animals such as poultry and pigs, and feed for insects.
  • Non-limiting examples of feed ingredients are poultry meal, fish meal, insect meal and PUFA-containing oil.
  • PUFA(s) means polyunsaturated fatty acid(s) such as docosahexaenoic acid (“DHA”) and/or eicosapentaenoic acid (“EPA”) and/or docosapentaenoic acid (“DPA”) and/or oleic acid and/or stearidonic acid and/or linoleic acid and/or alpha-linolenic acid (“ALA”) and/or gamma-linolenic acid and/or arachidonic acid (“ARA”) and/or the esters of all of them, whereby the term“esters” encompasses monoglycerides, diglycerides and triglycerides as well as Ci- 6 - alkyl esters such as especially the methyl esters and the ethyl esters, whereby the triglycerides are often dominant.
  • DHA docosahexaenoic acid
  • EPA eicosapentaenoic acid
  • DHA, EPA, ALA and stearidonic acid are omega-3 fatty acids, whereas linoleic acid, gamma-linolenic acid and ARA are omega-6 fatty acids.
  • DPA encompasses two isomers, the omega-3 fatty acid clupanodonic acid (7Z,10Z,13Z,16Z,19Z-docosapentaenoic acid) and the omega-6 fatty acid osbond acid (4Z,7Z,10Z,13Z,16Z-docosapentaenoic acid).
  • the polyunsaturated fatty acid (PUFA) is preferably DHA and/or EPA and/or DPA and/or any ester thereof, more preferably the polyunsaturated fatty acid (PUFA) is preferably DHA and/or EPA and/or any ester thereof.
  • - marine oil such as preferably fish oil
  • microbial oil containing polyunsaturated fatty acids and/or their esters
  • DHA docosahexaenoic acid
  • EPA eicosapentaenoic acid
  • DPA docosapentaenoic acid
  • DHA docosahexaenoic acid
  • EPA eicosapentaenoic acid
  • DPA docosapentaenoic acid
  • PUFA-containing plant oil such as e.g. canola seed oil, linseed/flaxseed oil, hempseed oil, pumpkin seed oil, evening primrose oil, borage seed oil, blackcurrent seed oil, sallow thorn/sea buckthorn oil, chia seed oil, argan oil and walnut oil.
  • feed ingredients such as especially poultry meal, fish meal, insect meal and PUFA enriched oil, comprising such compounds of formula
  • the present invention is directed to feed for aquatic animals comprising such compounds of formula (I) with the preferences as given above.
  • the present invention is also directed to feed for insects and terrestrial animals, e.g. pigs, poultry and pets, comprising such compounds of formula (I) with the preferences as given above.
  • Aquatic animals in the context of the present invention encompass farmed Crustacea such as shrimp and carnivorous species of farmed fish such as salmons, rainbow trout, brown trout (Salmo trutta) and gilthead seabream.
  • the feed for aquatic animals comprising the compounds of formula (I) are especially fed to the aquatic animals as cited above.
  • Feed ingredients are broadly classified into cereal grains, protein meals, fats and oils, minerals, feed additives, and miscellaneous raw materials, such as roots and tubers.
  • the compounds of formula (I) can be used in combination with one or more other antioxidants as described below.
  • the feed ingredients of the present invention additionally comprise a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol, which is known under the name“BHA” (butylated hydroxyanisole).
  • the feed ingredients of the present invention additionally comprise ascorbyl palmitate.
  • the feed ingredients of the present invention additionally comprise BHA and ascorbyl palmitate.
  • esters of ascorbic acid such as the esters of ascorbic acid with linear C 12-20 alkanols, preferably the esters of ascorbic acid with linear C 14-18 alkanols, may also be used, so that further embodiments of the present invention are directed to feed ingredients that additionally comprise esters of ascorbic acid with linear C 12-20 alkanols, preferably esters of ascorbic acid with linear C 14-18 alkanols, more preferably ascorbyl palmitate, whereby optionally BHA may also be present.
  • the feed ingredients may also comprise additionally alpha-tocopherol and/or gamma-tocopherol, whereby either an ester of ascorbic acid with a linear C 12 - 20 alkanol with the preferences as given above or BHA or both may additionally be present.
  • PUFAs polyunsaturated fatty acids
  • DHA docosahexaenoic acid
  • EPA eicosapentaenoic acid
  • DPA docosapentaenoic acid
  • - oil containing high amounts of PUFAs especially containing high amounts of DHA and/or EPA and/or DPA and/or their esters extracted from microbial biomass as e.g., fungi (“fungal oil”) or algae (“algal oil”);
  • PUFA- containing plant oil such as e.g. canola seed oil, linseed/flaxseed oil, hempseed oil, pumpkin seed oil, evening primrose oil, borage seed oil, blackcurrent seed oil, sallow thorn/sea buckthorn oil, chia seed oil, argan oil and walnut oil.
  • DHA does not only encompass the acid but also derivatives thereof such as monoglycerides, diglycerides and triglycerides as well as Ci- 6 -alkyl esters such as the methyl and ethyl esters.
  • EPA monoglycerides
  • DPA dihydroxyacetyl acetate
  • biomass such as especially fungal oil
  • feed ingredients may not only be used as alternative of fish oil and algal oil, but also in addition.
  • Suitable marine oils include, but are not limited to, Atlantic fish oil, Pacific fish oil, or Mediterranean fish oil, or any mixture or combination thereof.
  • a suitable fish oil can be, but is not limited to, pollack oil, bonito oil, pilchard oil, tilapia oil, tuna oil, sea bass oil, halibut oil, spearfish oil, barracuda oil, cod oil, menhaden oil, sardine oil, anchovy oil, capelin oil, herring oil, mackerel oil, salmonid oil, tuna oil, and shark oil, including any mixture or combination thereof.
  • marine oils suitable for use herein include, but are not limited to, squid oil, cuttle fish oil, octopus oil, krill oil, seal oil, whale oil, and the like, including any mixture or combination thereof.
  • an amount of at least one compound of formula (I) ranging from 10 to 500 ppm, preferably ranging from 30 to 300 ppm, more preferably ranging from 100 to 250 ppm, based on the total amount of the marine oil is usually sufficient.
  • PUFA- containing oils such as microbial oil, algal oil, fungal oil and PUFA-containing plant oil.
  • a commercially available example of marine oil is the fish oil “MEG-3” (Bleached 30S TG Fish oil) from DSM Nutritional Products, LLC (US) whose specification and composition is shown in Tables I and II below:
  • the peroxide value is defined as the amount of peroxide oxygen per 1 kilogram of oil. Traditionally this is expressed in units of milliequivalents or meq/kg.
  • Winterization is part of the processing of fish oil, and it is performed to remove solid fat in the oil.
  • The“cold test” is performed to check if any solid fat is present and precipitated in the oil when cooled to 0°C within a specific period of time. In this fish oil (Product Code: FG30TG), any such precipitation is checked for 3 hours at 0°C.
  • Algal oil is an oil containing high amounts of DHA and/or EPA and/or DPA and/or their esters extracted from algae as microbial source/biomass.
  • An example of algal oil is the commercially available“Algal oil containing EPA+DPA” from DSM Nutritional Products, LLC (US) whose composition is shown in the Table III below: Table III
  • a further example of a crude oil containing high amounts of DHA and/or EPA extracted from microbial sources as e.g., algae, is the oil extracted from Algae Schizochytrium Biomass, whose specification is given in the following
  • Microbial biomass containing polyunsaturated fatty acids especially docosahexaenoic acid and/or eicosapentaenoic acid and/or docosapentaenoic acid (“DPA”) and/or their esters
  • the biomass preferably comprises cells which produce PUFAs hetero- trophically.
  • the cells are preferably selected from algae, fungi, particularly yeasts, bacteria, or protists.
  • the cells are more preferably microbial algae or fungi.
  • Suitable cells of oil-producing yeasts are, in particular, strains of Yarrowia, Candida, Rhodotorula, Rhodosporidium, Cryptococcus, Trichosporon and Lipomyces.
  • Oil produced by a microorganism or obtained from a microbial cell is referred to as“microbial oil”.
  • Oil produced by algae and/or fungi is referred to as an algal and/or a fungal oil, respectively.
  • microorganism refers to organisms such as algae, bacteria, fungi, protist, yeast, and combinations thereof, e.g., unicellular organisms.
  • a microorganism includes but is not limited to, golden algae (e.g., microorganisms of the kingdom Stramenopiles); green algae; diatoms; dinoflagellates (e.g., microorganisms of the order Dinophyceae including members of the genus Crypthecodinium such as, for example,
  • microorganisms of the kingdom Stramenopiles may in particular be selected from the following groups of microorganisms: Hamatores, Proteromonads, Opalines, Developayella, Diplophrys,
  • the microorganisms are from the genus Mortierella, genus Crypthecodinium, genus Thraustochytrium, and mixtures thereof. In a further embodiment, the microorganisms are from Crypthecodinium Cohnii. In a further embodiment, the microorganisms are from Mortierella alpina. In a still further embodiment, the microorganisms are from
  • the microorganisms are selected from Crypthecodinium Cohnii, Mortierella alpina,
  • the microorganisms include, but are not limited to, microorganisms belonging to the genus Mortierella, genus Conidiobolus, genus Pythium, genus Phytophthora, genus Penicillium, genus Clodosporium, genus Mucor, genus Fusarium, genus Aspergillus, genus Rhodotorula, genus Entomophthora, genus Echinosporongium, and genus Saprolegnia.
  • the microorganisms are from microalgae of the order Thraustochytriales, which includes, but is not limited to, the genera Thraustochytrium (species include arudimentale, aureum, benthicola, globosum, kinnei, motivum, multirudimentole, pachydermum, proliferum, roseum, striatum); the genera Schizochytrium (species include aggregatum, limnaceum, mangrovei, minutum, octosporum); the genera Ulkenia (species include amoeboidea, kerguelensis, minuta, profunda, radiate, sailens, sarkariana, schizochytrops, visurgensis, yorkensis); the genera Aurantiacochytrium ; the genera Oblongichytrium ; the genera Sicyoidochytium ; the genera Parientichytrium ; the genera Botryochytrium ;
  • the microorganisms are from the order Thraustochytriales. In yet another embodiment, the microorganisms are from Thraustochytrium.
  • the microorganisms are from Schizochytrium sp.
  • the oil can comprise a marine oil.
  • suitable marine oils are the ones as given above.
  • the biomass according to the invention preferably comprises cells, and preferably consists essentially of such cells, of the taxon
  • Labyrinthulomycetes Labyrinthulea , net slime fungi, slime nets), in particular, those from the family of Thraustochytriaceae .
  • the family of the Thraustochytriaceae includes the genera Althomia, Aplanochytrium, Aurantiochytrium, Botryochytrium, Elnia, Japonochytrium, Oblongichytrium, Parietichytrium, Schizochytrium, Sicyoidochytrium, Thraustochytrium, and Ulkenia.
  • the biomass particularly preferably comprises cells from the genera Aurantiochytrium, Oblongichytrium, Schizochytrium, or Thraustochytrium, more preferably from the genus Schizochytrium.
  • the polyunsaturated fatty acid is preferably DHA and/or EPA and/or their esters as defined above.
  • the cells present in the biomass are preferably distinguished by the fact that they contain at least 20 weight-%, preferably at least 30 weight-%, in particular at least 35 weight-%, of PUFAs, in each case based on cell dry matter.
  • cells in particular a Schizochytrium strain, is employed which produces a significant amount of EPA and DHA, simultaneously, wherein DHA is preferably produced in an amount of at least 20 weight-%, preferably in an amount of at least 30 weight-%, in particular in an amount of 30 to 50 weight-%, and EPA is produced in an amount of at least 5 weight-%, preferably in an amount of at least 10 weight-%, in particular in an amount of 10 to 20 weight-% (in relation to the total amount of lipid as contained in the cells, respectively).
  • PTA-10208 PTA-10209, PTA-10210, or PTA-10211 , PTA-10212, PTA-10213, PTA-10214, PTA-10215.
  • DHA and EPA producing Schizochytrium strains can be obtained by consecutive mutagenesis followed by suitable selection of mutant strains which demonstrate superior EPA and DHA production and a specific EPA:DHA ratio.
  • Any chemical or nonchemical (e.g. ultraviolet (UV) radiation) agent capable of inducing genetic change to the yeast cell can be used as the mutagen.
  • UV radiation ultraviolet
  • These agents can be used alone or in combination with one another, and the chemical agents can be used neat or with a solvent.
  • Methods for producing the biomass in particular, a biomass which comprises cells containing lipids, in particular PUFAs, particularly of the order
  • Thraustochytriales are described in detail in the prior art (see e.g. WO 91 /07498, WO 94/08467, WO 97/37032, WO 97/36996, WO 01 /54510).
  • the production takes place by cells being cultured in a fermenter in the presence of a carbon source and a nitrogen source, along with a number of additional substances like minerals that allow growth of the
  • biomass densities of more than 100 grams per litre and production rates of more than 0.5 gram of lipid per litre per hour may be attained.
  • the process is preferably carried out in what is known as a fed-batch process, i.e. the carbon and nitrogen sources are fed in incrementally during the
  • production may be induced by various measures, for example by limiting the nitrogen source, the carbon source or the oxygen content or combinations of these.
  • the cells are grown until they reach a biomass density of at least 80 or 100 g/l, more preferably at least 120 or 140 g/l, in particular at least 160 or 180 g/l (calculated as dry-matter content).
  • a biomass density of at least 80 or 100 g/l, more preferably at least 120 or 140 g/l, in particular at least 160 or 180 g/l (calculated as dry-matter content).
  • the cells are fermented in a medium with low salinity, in particular, so as to avoid corrosion.
  • This can be achieved by using chlorine- free sodium salts as the sodium source instead of sodium chloride, such as, for example, sodium sulphate, sodium carbonate, sodium hydrogen carbonate or soda ash.
  • chloride is used in the fermentation in amounts of less than 3 g/l, in particular, less than 500 mg/l, especially preferably less than 100 mg/l.
  • PUFA-containing plant oils Plant oils with relatively high amounts of PUFAs, especially with high amounts of DHA and/or EPA such as e.g. , canola seed oil
  • the plant cells may, in particular, be selected from cells of the families Brassicaceae, Elaeagnaceae and Fabaceae.
  • Brassicaceae may be selected from the genus Brassica, in particular, from oilseed rape, turnip rape and Indian mustard; the cells of the family
  • Elaeagnaceae may be selected from the genus Elaeagnus, in particular, from the species Oleae europaea ; the cells of the family Fabaceae may be selected from the genus Glycine, in particular, from the species Glycine max. Examples:
  • - Canola seed oil with a content of EPA of at least 9% by weight, of at least 12% by weight, of at least 15% by weight, or of at least 20% by weight, based on the total weight of the canola seed oil.
  • PUFA-containing plant oils containing high amounts of other PUFAs than EPA and/or DHA and/or DPA and/or their esters are linseed/flaxseed oil, hempseed oil, pumpkin seed oil, evening primrose oil, borage seed oil, blackcurrent seed oil, sallow thorn/sea buckthorn oil, chia seed oil, argan oil and walnut oil.
  • Poultry meal is a high-protein commodity used as a feed ingredient. It is made from grinding clean, rendered parts of poultry carcasses and can contain bones, offal, undeveloped eggs, and some feathers. Poultry meal quality and composition can change from one batch to another.
  • Chicken meal like poultry meal, is made of "dry, ground, rendered clean parts of the chicken carcass" according to AAFCO and may contain the same ingredients as poultry meal. Chicken meal can vary in quality from batch to batch. Chicken meal costs less than chicken muscle meat and lacks the digestibility of chicken muscle meat.
  • Poultry meal contains preferably not less than 50 weight-% of crude protein, not less than 5 weight-% of crude fat, not more than 5 weight-% of crude fiber, not more than 40 weight-% of ash and not more than 15 weight-% of water, each based on the total weight of the poultry meal, whereby the total amount of all ingredients sums up to 100 weight-%.
  • poultry meal contains from 50 to 85 weight-% of crude protein, and from 5 to 20 weight-% of crude fat, and from 1 to 5 weight-% of crude fiber, and from 5 to 40 weight-% of ash, and from 5 to 15 weight-% of water, each based on the total weight of the poultry meal, whereby the total amount of all ingredients sums up to 100 weight-%.
  • Fish meal contains preferably not less than 50 weight-% of crude protein, and not more than 20 weight-% of crude fat, and not more than 10 weight-% of crude fibers, and not more than 25 weight-% of ash, and not more than 15 weight-% of water, each based on the total weight of the fish meal, whereby the total amount of all ingredients sums up to 100 weight-%.
  • More preferably fish meal contains from 50 to 90 weight-% of crude protein and from 5 to 20 weight-% of crude fat, and from 1 to 10 weight-% of crude fibers, and from 5 to 25 weight-% of ash, and from 5 to 15 weight-% of water, each based on the total weight of the fish meal, whereby the total amount of all ingredients sums up to 100 weight-%.
  • At least one compound of formula (I) ranging from 10 to 2000 ppm, preferably ranging from 100 to 1500 ppm, more preferably ranging from 300 to 1000 ppm, based on the total amount of the fish meal, is usually sufficient.
  • Fish meal is a commercial product made from fish that is used primarily as a protein supplement in compound feed, especially for feeding farmed fish, Crustacea, pigs and poultry, and companion animals such as cats and dogs.
  • a portion of the fish meal is made from the bones and offal left over from processing fish used for human consumption, while the larger percentage is manufactured from wild-caught, small marine fish. It is powder or cake obtained by drying the fish or fish trimmings, often after cooking, and then grinding it. If the fish used is a fatty fish it is first pressed to extract most of the fish oil.
  • fish meal The uses and need of fish meal are increasing due to the rising demand for fish, because fish has the best feed conversion rate of all farmed animals, can be produced well in developing countries and has a small size, i.e. can be slaughtered for preparing a meal, so that there is no need to store the fish. Furthermore, there are no religious constraints concerning the consumption of fish, fish is a source of high quality protein and it is easy to digest.
  • Fish meal is made by cooking, pressing, drying, and grinding of fish or fish waste to which no other matter has been added. It is a solid product from which most of the water is removed and some or all of the oil is removed. About four or five tons of fish are needed to manufacture one ton of dry fish meal.
  • Cooking A commercial cooker is a long, steam -jacketed cylinder through which the fish are moved by a screw conveyor. This is a critical stage in preparing the fishmeal, as incomplete cooking means the liquid from the fish cannot be pressed out satisfactorily and overcooking makes the material too soft for pressing. No drying occurs in the cooking stage.
  • Pressing A perforated tube with increasing pressure is used for this process. This stage involves removing some of the oil and water from the material and the solid is known as press cake. The water content in pressing is reduced from 70% to about 50% and oil is reduced to 4%.
  • the two main types of dryers are:
  • Indirect A cylinder containing steam-heated discs is used, which also tumbles the meal.
  • the fish meal has to be transported long distances by ship or other vehicles to the various locations, where it is used.
  • Unmodified fish meal can spontaneously combust from heat generated by oxidation of the polyunsaturated fatty acids in the fish meal. Therefore, it has to be stabilized by antioxidants. Especially advantageous for this purpose are the compounds of formula (I) of the present invention.
  • Insect meal is a compound of formula (I) of the present invention.
  • Insect meal has a high content of protein and is therefore, a valuable source of protein.
  • insects of special interest in the context of the present invention encompass black soldier flies (Hermetia species, commonly called BSF), mealworms (Tenebrio molitor), lesser mealworms (Alphitobius diaperinus), house cricket (Acheta domesticus, grasshoppers (Locusta migratoria), buffaloworms (Alphitobius diaperinus), cockroaches and domestic flies, whereby black soldier flies (Hermetia species, commonly called BSF), mealworms (Tenebrio molitor) and lesser mealworms (Alphitobius diaperinus) are more preferred.
  • the compounds of formula (I) are not only suitable for stabilizing feed ingredients such as poultry meal, fish meal, insect meal and PUFA- containing oil, but also effective antioxidants for feed.
  • Feed means any substance or product, including additives, whether processed, partially processed or unprocessed, intended to be used for oral feeding to animals.
  • Feed in the context of the present invention is feed for aquatic animals and for terrestrial animals, as well as feed for insects.
  • the compounds of formula (I) can be used in combination with one or more other antioxidants as described below.
  • the feed of the present invention additionally comprises a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert- butyl-4-methoxyphenol, which is known under the name“BHA” (butylated hydroxyanisole).
  • the feed of the present invention additionally comprises ascorbyl palmitate.
  • the feed of the present invention additionally comprises BHA and ascorbyl palmitate.
  • esters of ascorbic acid such as the esters of ascorbic acid with linear C12-20 alkanols, preferably the esters of ascorbic acid with linear Ci 4 -is alkanols, may also be used, so that further embodiments of the present invention are directed to feed that additionally comprises esters of ascorbic acid with linear C12-20 alkanols, preferably esters of ascorbic acid with linear Ci 4- 18 alkanols, more preferably ascorbyl palmitate, whereby optionally BHA may also be present.
  • the feed may also comprise additionally alpha-tocopherol and/or gamma- tocopherol, whereby either an ester of ascorbic acid with a linear C12-20 alkanol with the preferences as given above or BHA or both may additionally be present.
  • the feed for poultry differs from region to region.
  • Tables V and VI typical examples for diets in Europe and Latin America are given. These diets include cereals such as wheat, rye, maize/corn, minerals such as NaCl, vegetable oils such as soya oil, amino acids and proteins.
  • Pet foods are formulated to meet nutrient specifications using combinations of multiple ingredients to meet the targeted nutrient specification.
  • Poultry meal e.g. is an ingredient that is commonly found in Dog and Cat foods.
  • the nutrient specifications for a complete and balanced dog or cat food will meet or exceed the guidelines provided by AAFCO (American Association of Feed Control Officials).
  • the ingredient composition of pet-food can include any legal feed ingredient so number of combinations are not quite infinite but close.
  • a typical example of feed for fish comprises the following ingredients, whereby all amounts are given in weight-%, based on the total weight of the feed for fish:
  • - binders mainly starch, in an amount ranging from 9 to 12 weight-%;
  • micro-ingredients such as vitamins, choline, minerals, mono calcium phosphate (“MCP”) and/or amino acids in an amount ranging from 3 to 6 weight-%;
  • marine oil in an amount ranging from 5 to 10 weight-%, preferably marine oil in said amount comprising the compounds of formula (I) of the present invention
  • R 1 and R 3 are independently from each other H or methyl, and R 2 is either H or methyl or methoxy, and
  • the first of the two solvents is selected from ethylene carbonate, propylene carbonate, 1 ,2-butylene carbonate, gamma-butyrolactone and water
  • the second of the two solvents is selected from hexane, cyclohexane, heptane, ortho-xylene, meta-xylene, para-xylene, mesitylene,
  • pseudocumene methyl tert- butyl ether, and toluene.
  • the first of the two solvents is ethylene carbonate or propylene carbonate
  • the second of the two solvents is selected from either hexane, cyclohexane or heptane. More preferably the first of the two solvents is ethylene carbonate and the second of the two solvents is heptane.
  • hexane encompasses n -hexane, as well as any mixture of the isomers of hexane. The same applies for heptane.
  • the volume ratio of the first solvent to the second solvent during the reaction is in the range of 1 :4 to 4:1 , more preferably the volume ratio of the first solvent to the second solvent is in the range of 1 :3 to 3:1 most preferably the volume ratio of the first solvent to the second solvent is in the range of 1 :2 to 2:1 .
  • the total amount of the two solvents is in the range of 1 to 10 kg, more preferably in the range of 2 to 7 kg, most preferably in the range of 2.5 to 6 kg, per kg of the compound of formula (II).
  • the acid catalyst is preferably selected from Bronsted acids, Lewis acids and any mixtures thereof.
  • Bronsted acids are sulfuric acid, phosphoric acid, acidic ion-exchange resins, acidic clays, zeolites, hydrochloric acid, trifluoroacetic acid, trichloroacetic acid, acetic acid, formic acid, methanesulfonic acid, benzenesulfonic acid, para-toluenesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, bis(perfluoroalkyl- sulfonyl)methanes (R’S0 2 )(R”S0 2 )CH 2 wherein R’ and R” each signify independently from each other a perfluoroalkyl group of the formula C n F 2n+i where n is an integer from 1 to 10, tris(perfluorosulfonyl)methanes
  • R’ independently from each other a perfluoroalkyl group of the formula C n F 2n+i where n is an integer from 1 to 10, and whereby at least two of R’, R” and R’” are identical perfluoroalkyl groups, or R’ signifies the pentafluorophenyl group (-C 6 F 5 ) and R” and R’” each signify an identical perfluoroalkyl group of the above formula C n F 2n+i , methanetrisulfonic acid, and
  • Lewis acids examples include Al(OTf) 3 , Sc(OTf) 3 , Sc(NTf 2 ) 3 , ScCl 3 , Yb(OTf) 3 , YbCl 3 , Cu(OTf) 2 , FeCl 2 , Fe(OTf) 2 , ZnCl 2 , Zn(OTf) 2 , Zn(NTf 2 ) 3 , YCl 3 , Y(OTf) 3 , lnCl 3 , lnBr 3 , ln(OTf) 3 , ln(NTf 2 ) 3 , La(OTf) 3 , Ce(OTf) 3 , Sm(OTf) 3 , Gd(OTf) 3 and Bi(OTf)3 in the presence or absence of 2,2-bipyridine and any mixture thereof, whereby the use of single catalysts is preferred.
  • the acid catalyst is para-toluenesulfonic acid, sulfuric acid, methanesulfonic acid, Al(OTf) 3 , Sc(OTf) 3 , or ln(OTf) 3 , most preferably the acid catalyst is para-toluenesulfonic acid or Al(OTf) 3 .
  • the amount of the acid catalyst is in the range of 0.001 to 5 mol equivalents, more preferably in the range of 0.005 to 1 mol equivalents, most preferably in the range of 0.01 to 0.1 mol equivalents, relative to the amount of compound of formula (III).
  • the molar ratio of the compound of formula (II) to the compound of formula (III) is in the range of 6.0:1 to 1 .1 :1 , more preferably it is in the range of 4.0:1 to 1 .2: 1 , even more preferably it is in the range of from 3.0:1 to 1 .3: 1 , most preferably it is in the range of 2.0:1 to 1.5:1 .
  • the reaction is preferably carried out at a temperature in the range of 70 to 160°C, more preferably in the range of 80 to 130°C, most preferably in the range of 90-105°C.
  • the reaction is preferably carried out at a pressure in the range of 0.8 to 20 bar (absolute), more preferably at a pressure in the range of 0.8 to 10 bar (absolute), most preferably at a pressure in the range of 0.8 to 5 bar (absolute).
  • An advantage of the process according to the present invention is that the acid catalyst is reusable.
  • all embodiments with regard to the reaction conditions and the preferences as given above are realized.
  • R,R,R- delta-tocopherol (compound of formula (1A)) is commercially available, e.g. from Sigma-Aldrich, Product no. T2028, (+)-d-tocopherol, >90%.
  • Oxidative stability was assessed using an Oxipres (Mikrolab Aarhus A/S, Hojbjerg, Denmark).
  • the ML OXIPRES® is designed to monitor the oxidation of heterogeneous products. Consumption of oxygen results in a pressure drop which is measured by means of pressure transducers. The samples are heated to accelerate the process and shorten the analysis time (Mikrolab Aarhus 2012).
  • Sample weights were 50 g. They were loaded into the Oxipres vessels and placed inside the stainless-steel pressure vessel and sealed. The pressure vessels were purged with pure oxygen and filled to an initial oxygen pressure of 5 bar and maintained at 70° C during measurement (D. Ying, L. Edin, L. Cheng, L. Sanguansri, M. A. Augustin, LWT - Food Science and Technology 2015, 62, 1105-1 11 1 :“Enhanced oxidative stability of extruded product containing polyunsaturated oils.”).
  • the oxygen pressure was recorded as function of time. After sample load and temperature rise the pressure in the device is increasing within 10 hours. Thereafter it is decreasing. Consequently, the starting pressure is considered as being the pressure that is achieved after 10 hours. The analysis ends after 130 hours at 70°C.
  • the oxygen consumption‘0 2 ’ of the tested sample is calculated as follows:
  • EV Efficacy Value
  • pet food, poultry meal and fish meal have been used as feed application with the composition as given in the following table 2.
  • the EV of BHT is 1.0 in all three matrices, the EVs of alpha-tocopherol are shown in Table 3 below.
  • An efficacy value > 0.6 is considered as acceptable, an efficacy value equal or greater to the one of alpha-tocopherol as good, and an efficacy value equal or greater to the one of BHT as very good.
  • Compound of formula (1A) was mixed into each matrix 1 , 2 or 3 (pet food, poultry meal, fish meal) in an equimolar ratio compared to BHT. Batches of 200 g feed were produced in order to handle a minimum of 30 mg of antioxidant. First, a 1% pre-dilution of the antioxidant with the feed material was made. Then this pre-dilution was added to the final batch, mixed, sieved (1 .25 mm sieve) and mixed using a turbula® mixer.
  • results obtained from pet food samples are shown in the following Table 4.
  • results obtained from poultry meal samples are shown in the following Table 5.
  • Results obtained from fish meal samples are shown in the following Table 6.
  • Example 3 Antioxidant activities of compound of formula (2) in fish oil and algal oil
  • Antioxidant effect was determined using
  • PV peroxide value
  • OSI values of the fish oil samples containing compound of formula (2), in comparison to the same levels of MNT, are shown in Table 7 and 8.
  • OSI values and Protection Factors (PF) of the algal oil samples containing compound of formula (2), in comparison to the same levels of MNT are shown in Table 9 and 10.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Feed For Specific Animals (AREA)
  • Fodder In General (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Abstract

La présente invention concerne l'utilisation de chroman-6-ols substitués à chaînes latérales lipophiles étendues de formule (I) où l'un des deux substituants R1 et R2 est un alkyle en C12-21 et l'autre desdits deux substituants R1 et R2 est soit un atome d'hydrogène, soit un alkyle en C1-5 ou (CH2)n-OH, n étant un nombre entier de 1 à 5, et où A est CH(R3), et R3, R4 et R6 sont indépendamment les uns des autres H ou un alkyle en C1-4, et R5 est H ou OH ou un alkyle en C1-4 ou un alcoxy en C1-4 ; à condition qu'au moins deux des R4, R5 et R6 ne soient pas méthyle quand R3 est H et que l'un des substituants R1 et R2 soit méthyle et l'autre des deux substituants R1 et R2 soit un alkyle en C12-21, à titre d'antioxydants, notamment dans des aliments pour animaux de compagnie et les ingrédients alimentaires tels que la farine pour poissons, la farine pour insectes et la farine pour volaille, ainsi que dans l'huile contenant des AGPI comme l'huile marine, l'huile microbienne, l'huile fongique, l'huile algale et l'huile végétale contenant des AGPI. Des ingrédients alimentaires et des aliments pour insectes, animaux aquatiques et terrestres comprenant lesdits chroman-6-ols substitués à chaînes latérales lipophiles étendues de formule (I) sont en outre décrits.
PCT/EP2019/058117 2018-03-29 2019-03-29 Nouvelle utilisation des chroman-6-ols substitués à chaînes latérales lipophiles étendues WO2019185938A2 (fr)

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BR112020019757-2A BR112020019757A2 (pt) 2018-03-29 2019-03-29 uso inovador de croman-6-óis substituídos com cadeias laterais lipofílicas estendidas
PE2020001504A PE20211652A1 (es) 2018-03-29 2019-03-29 Uso novedoso de croman-6-oles sustituidos con cadenas laterales lipofilicas extendidas
US17/041,910 US11447459B2 (en) 2018-03-29 2019-03-29 Use of substituted chroman-6-ols with extended lipophilic side chains
EP19715068.3A EP3774758A2 (fr) 2018-03-29 2019-03-29 Nouvelle utilisation des chroman-6-ols substitués à chaînes latérales lipophiles étendues

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WO2022078924A1 (fr) 2020-10-12 2022-04-21 Dsm Ip Assets B.V. Nouveaux additifs alimentaires de vitamines liposolubles
WO2022112585A1 (fr) 2020-11-30 2022-06-02 Dsm Ip Assets B.V. Nouvelles formulations sans sucre, leur fabrication et leur utilisation
WO2022112592A1 (fr) 2020-11-30 2022-06-02 Dsm Ip Assets B.V. Nouvelles formulations à teneur réduite en antioxydant, leur fabrication et leur utilisation
WO2022112586A1 (fr) 2020-11-30 2022-06-02 Dsm Ip Assets B.V. Nouvelles formulations sans sucre, leur production et leur utilisation
WO2022112587A1 (fr) 2020-11-30 2022-06-02 Dsm Ip Assets B.V. Nouvelles formulations à teneur réduite en antioxydant, leur production et leur utilisation
WO2022129433A1 (fr) 2020-12-18 2022-06-23 Dsm Ip Assets B.V. Lait de remplacement comprenant des formulations sans matière animale de vitamines liposolubles
WO2022129435A1 (fr) 2020-12-18 2022-06-23 Dsm Ip Assets B.V. Succédané de lait comportant des formulations d'origine non animale de vitamines liposolubles

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WO2022078924A1 (fr) 2020-10-12 2022-04-21 Dsm Ip Assets B.V. Nouveaux additifs alimentaires de vitamines liposolubles
WO2022112585A1 (fr) 2020-11-30 2022-06-02 Dsm Ip Assets B.V. Nouvelles formulations sans sucre, leur fabrication et leur utilisation
WO2022112592A1 (fr) 2020-11-30 2022-06-02 Dsm Ip Assets B.V. Nouvelles formulations à teneur réduite en antioxydant, leur fabrication et leur utilisation
WO2022112586A1 (fr) 2020-11-30 2022-06-02 Dsm Ip Assets B.V. Nouvelles formulations sans sucre, leur production et leur utilisation
WO2022112587A1 (fr) 2020-11-30 2022-06-02 Dsm Ip Assets B.V. Nouvelles formulations à teneur réduite en antioxydant, leur production et leur utilisation
WO2022129433A1 (fr) 2020-12-18 2022-06-23 Dsm Ip Assets B.V. Lait de remplacement comprenant des formulations sans matière animale de vitamines liposolubles
WO2022129435A1 (fr) 2020-12-18 2022-06-23 Dsm Ip Assets B.V. Succédané de lait comportant des formulations d'origine non animale de vitamines liposolubles

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US20210130314A1 (en) 2021-05-06
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